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Issue 15, 2009
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Constructing clusters with enhanced magnetic properties by assembling and distorting Mn3 building blocks

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Abstract

The reaction of Mn(ClO4)2·6H2O with Naphth-saoH2 (Naphth-saoH2 = 2-hydroxy-1-napthaldoxime) in pyridine (py) forms the complex [MnIII3O(Naphth-sao)3(py)3](ClO4)·0.5py (1·0.5py) in very good yields. Reaction of 1 with NaO2CPh in EtOH produces the complex [MnIII6O2(Naphth-sao)6(O2CPh)2(EtOH)6]·[MnIII6O2(Naphth-sao)6(O2CPh)2(EtOH)4]·2.5Et2O·0.5H2O (2·2.5Et2O·0.5H2O). Further reaction of complex 2 with 1 equivalent of both NaN3 and Mn(ClO4)2·6H2O in MeOH produces the complex [MnII2MnIII6O2(Naphth-sao)6(N3)6(MeOH)8]·10MeOH (3·10MeOH) that displays an S≈ 0 ground state. Ligand substitution of Naphth-saoH2 with Me-saoH2 in CH2Cl2MeOH for the latter complex (Me-saoH2= 2-hydroxyphenylethanone oxime) forms the complex [MnII2MnIII6O2(Me-sao)6(N3)6(MeOH)8]·10MeOH (4·10MeOH) that displays an S = 7 ground state with Ueff= 44.6 K. In all four complexes the main building block is the triangular {MnIII3O(R-sao)3} unit (R = Naphth for 1, 2 and 3; R = Me for 4). The ligand substitution in 3 triggers a structural distortion in the [Mn6] sub-core as observed by the increased (Mn–N–O–Mn) torsion angles in 4, switching the interactions from antiferro- to ferromagnetic, dramatically changing the ground-state of the octanuclear complexes from S = 0 to 7.

Graphical abstract: Constructing clusters with enhanced magnetic properties by assembling and distorting Mn3 building blocks

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Publication details

The article was received on 14 Nov 2008, accepted on 23 Jan 2009 and first published on 24 Feb 2009


Article type: Paper
DOI: 10.1039/B820362H
Citation: Dalton Trans., 2009, 2812-2822
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    Constructing clusters with enhanced magnetic properties by assembling and distorting Mn3 building blocks

    C. J. Milios, R. Inglis, L. F. Jones, A. Prescimone, S. Parsons, W. Wernsdorfer and E. K. Brechin, Dalton Trans., 2009, 2812
    DOI: 10.1039/B820362H

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